Utilizing a multiphase reactor for the conversion of biomass to produce substituted furans

Abstract

The present disclosure provides methods to produce substituted furans (e.g., halomethylfurfural, hydroxymethylfurfural, and furfural), by acid-catalyzed conversion of biomass using a gaseous acid in a multiphase reactor, such as a fluidized bed reactor.

What is claimed is: 
     
       1. A method for producing a hydroxymethylfurfural in a gas-solid phase reactor, the method comprising:
 feeding solid feedstock into a gas-solid phase reactor, wherein the solid feedstock comprises biomass or sugar, or any combination thereof; 
 feeding gaseous acid into the gas-solid phase reactor, wherein the gaseous acid has less than about 10% by weight of water; 
 mixing the solid feedstock and the gaseous acid to form a reaction mixture; 
 adding lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, aluminum chloride, or boron chloride, or any combination thereof, to the reaction mixture; and 
 producing a hydroxymethylfurfural from at least a portion of the solid feedstock and at least a portion of the gaseous acid in the reaction mixture. 
 
     
     
       2. The method of  claim 1 , wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, and wherein the unreacted gaseous acid comprises water, and the method further comprises:
 separating the unreacted gaseous acid from the reaction mixture using a solid-gas separator; and 
 drying the separated unreacted gaseous acid to remove at least a portion of the water in the separated unreacted gaseous acid. 
 
     
     
       3. The method of  claim 2 , further comprising feeding the dried separated unreacted gaseous acid into the gas-solid phase reactor. 
     
     
       4. The method of  claim 1 , wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, or at least a portion of the solid feedstock in the reaction mixture is unreacted solid feedstock, or a combination thereof, and the method further comprises:
 separating the hydroxymethylfurfural produced from the unreacted gaseous acid or the unreacted solid feedstock, or a combination thereof, using a solvent, wherein the solvent solubilizes at least a portion of the hydroxymethylfurfural. 
 
     
     
       5. The method of  claim 4 , wherein the solvent is selected from the group consisting of dichloromethane, ethylacetate, hexane, cyclohexane, benzene, toluene, diethyl ether, tetrahydrofuran, acetone, dimethyl formamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol, isopropanol, n-propanol, n-butanol, chloroform, dichloroethane, trichloroethane, furfural, furfuryl alcohol, supercritical carbon dioxide, and any combination thereof. 
     
     
       6. The method of  claim 1 , wherein the gas-solid phase reactor is a fluidized bed reactor. 
     
     
       7. The method of  claim 1 , wherein the gaseous acid is a halogen-based mineral acid or a halogen-based organic acid. 
     
     
       8. The method of  claim 1 , wherein the gaseous acid is hydrochloric acid. 
     
     
       9. The method of  claim 1 , wherein the biomass comprises glycans. 
     
     
       10. The method of  claim 1 , wherein the biomass comprises heteroglycans. 
     
     
       11. The method of  claim 1 , wherein the hydroxymethylfurfural is 5-(hydroxymethyl)furfural. 
     
     
       12. A method for producing a hydroxymethylfurfural in a gas-solid phase reactor, the method comprising:
 feeding solid feedstock and gaseous acid into a gas-solid phase reactor, wherein the solid feedstock comprises biomass or sugar, or any combination thereof; 
 mixing the solid feedstock and the gaseous acid in the presence of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, aluminum chloride, or boron chloride, or any combination thereof to form a reaction mixture, under conditions suitable to produce a hydroxymethylfurfural; and 
 producing a hydroxymethylfurfural from at least a portion of the solid feedstock and at least a portion of the gaseous acid in the reaction mixture, wherein the reaction mixture has less than 10% by weight of water. 
 
     
     
       13. The method of  claim 12 , wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, and wherein the unreacted gaseous acid comprises water, and the method further comprises:
 separating the unreacted gaseous acid from the reaction mixture using a solid-gas separator; and 
 drying the separated unreacted gaseous acid to remove at least a portion of the water in the separated unreacted gaseous acid. 
 
     
     
       14. The method of  claim 13 , further comprising feeding the dried separated unreacted gaseous acid into the gas-solid phase reactor. 
     
     
       15. The method of  claim 12 , wherein the gaseous acid is gaseous hydrochloric acid. 
     
     
       16. The method of  claim 12 , wherein the gaseous acid has less than 10% by weight of water. 
     
     
       17. The method of  claim 12 , wherein the hydroxymethylfurfural is 5-(hydroxymethyl)furfural. 
     
     
       18. The method of  claim 12 , wherein the gas-solid phase reactor is a fluidized bed reactor. 
     
     
       19. The method of  claim 12 , wherein the biomass comprises glycans. 
     
     
       20. The method of  claim 12 , wherein the biomass comprises heteroglycans. 
     
     
       21. A method for producing a hydroxymethylfurfural in a gas-solid phase reactor, the method comprising:
 feeding solid feedstock into a gas-solid phase reactor, wherein the solid feedstock comprises biomass or sugar, or any combination thereof; 
 feeding gaseous acid into the gas-solid phase reactor, wherein the gaseous acid has less than about 10% by weight of water; 
 mixing the solid feedstock and the gaseous acid to form a reaction mixture; 
 producing a hydroxymethylfurfural from at least a portion of the solid feedstock and at least a portion of the gaseous acid in the reaction mixture, wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, or at least a portion of the solid feedstock in the reaction mixture is unreacted solid feedstock, or a combination thereof; and 
 separating the hydroxymethylfurfural produced from the unreacted gaseous acid or the unreacted solid feedstock, or a combination thereof, using a solvent, wherein the solvent solubilizes at least a portion of the hydroxymethylfurfural. 
 
     
     
       22. The method of  claim 21 , wherein the solvent is selected from the group consisting of dichloromethane, ethylacetate, hexane, cyclohexane, benzene, toluene, diethyl ether, tetrahydrofuran, acetone, dimethyl formamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol, isopropanol, n-propanol, n-butanol, chloroform, dichloroethane, trichloroethane, furfural, furfuryl alcohol, supercritical carbon dioxide, and any combination thereof. 
     
     
       23. The method of  claim 21 , wherein the unreacted gaseous acid comprises water, and the method further comprises:
 separating the unreacted gaseous acid from the reaction mixture using a solid-gas separator; and 
 drying the separated unreacted gaseous acid to remove at least a portion of the water in the separated unreacted gaseous acid. 
 
     
     
       24. The method of  claim 23 , further comprising feeding the dried separated unreacted gaseous acid into the gas-solid phase reactor. 
     
     
       25. The method of  claim 21 , wherein the gas-solid phase reactor is a fluidized bed reactor. 
     
     
       26. The method of  claim 21 , wherein the gaseous acid is a halogen-based mineral acid or a halogen-based organic acid. 
     
     
       27. The method of  claim 21 , wherein the gaseous acid is hydrochloric acid. 
     
     
       28. The method of  claim 21 , wherein the biomass comprises glycans. 
     
     
       29. The method of  claim 21 , wherein the biomass comprises heteroglycans. 
     
     
       30. The method of  claim 21 , wherein the hydroxymethylfurfural is 5-(hydroxymethyl)furfural. 
     
     
       31. A method for producing a hydroxymethylfurfural in a gas-solid phase reactor, the method comprising:
 feeding solid feedstock and gaseous acid into a gas-solid phase reactor, wherein the solid feedstock comprises biomass or sugar, or any combination thereof; 
 mixing the solid feedstock and the gaseous acid to form a reaction mixture, under conditions suitable to produce a hydroxymethylfurfural; 
 producing a hydroxymethylfurfural from at least a portion of the solid feedstock and at least a portion of the gaseous acid in the reaction mixture, wherein the reaction mixture has less than 10% by weight of water and wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, or at least a portion of the solid feedstock in the reaction mixture is unreacted solid feedstock, or a combination thereof; and 
 separating the hydroxymethylfurfural produced from the unreacted gaseous acid or the unreacted solid feedstock, or a combination thereof, using a solvent, wherein the solvent solubilizes at least a portion of the hydroxymethylfurfural. 
 
     
     
       32. The method of  claim 31 , wherein the solvent is selected from the group consisting of dichloromethane, ethylacetate, hexane, cyclohexane, benzene, toluene, diethyl ether, tetrahydrofuran, acetone, dimethyl formamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol, isopropanol, n-propanol, n-butanol, chloroform, dichloroethane, trichloroethane, furfural, furfuryl alcohol, supercritical carbon dioxide, and any combination thereof. 
     
     
       33. The method of  claim 31 , wherein at least a portion of the gaseous acid in the reaction mixture is unreacted gaseous acid, and wherein the unreacted gaseous acid comprises water, and the method further comprises:
 separating the unreacted gaseous acid from the reaction mixture using a solid-gas separator; and 
 drying the separated unreacted gaseous acid to remove at least a portion of the water in the separated unreacted gaseous acid. 
 
     
     
       34. The method of  claim 31 , further comprising feeding the dried separated unreacted gaseous acid into the gas-solid phase reactor. 
     
     
       35. The method of  claim 31 , wherein the gaseous acid is gaseous hydrochloric acid. 
     
     
       36. The method of  claim 31 , wherein the gaseous acid has less than 10% by weight of water. 
     
     
       37. The method of  claim 31 , wherein the hydroxymethylfurfural is 5-(hydroxymethyl)furfural. 
     
     
       38. The method of  claim 31 , wherein the gas-solid phase reactor is a fluidized bed reactor. 
     
     
       39. The method of  claim 31 , wherein the biomass comprises glycans. 
     
     
       40. The method of  claim 31 , wherein the biomass comprises heteroglycans.